Polyurethanes of hydroxyaryl-aliphatic acid-aldehyde condensates



POLYURETHANES or HYDROXYARYL-ALI- PHATIC ACID-ALDEHYDE CONDENSATES Sylvan O. Greenlee, Racine, Wis., assignor to S. C.'Johnson & Son, Inc., Racine, Wis.

N Drawing. Application February 21, 1957 Serial No. 641,489

Claims. (Cl. 260'51) This invention relates to novel resinous compositions of matter of the polyurethane type and is directed more particularly to synthetic resinous compositions derived from the reaction of polyisocyanates with ahydroxyarylaliphatic acid-aldehyde condensation product.

One of the objects of this invention is to provide a new class of synthetic resinous compositions which are capable of further reaction to give infusible, insoluble materials suitable for use as protective coatings, adhesives, and molding resins.

A further object is the synthesis along the general lines of known reactions of a film-forming product characterized, by virtue of the novel reactants from which it is derived, With improved properties especially as regards resistance to attack by common chemicals, resistance to wear or damage, and resistance topenetration and solvent action by water.

By suitable adjustment of the conditions of the reac tion and the ingredients, the product of the invention may be caused to assume a cellular or foam state, and, ac-

"ice

in the formulation of protective coatings which are likely to be subjected in the course of ordinary usage to contact with various chemicals. The presence in the resin of residues having a symmetrical structure results in a more rigid product, a feature of much advantage in polyurethane foams. V

The hydroxyaryl-aliphatic acids used in the condensation may be, and preferably are, prepared by condensing a phenolic compound with a keto-acid under such con" ditions that two hydroxyaryl radicals are attached to the same carbon atom of the acid. In order for the yields of this reaction to achieve useful levels, it is necessary, first, that the keto-carbon atom occur at the position adjacent a terminal methyl group, and second, that the keto-acid have atleast five carbons in the aliphatic chain. The keto-acid of this type which has only four carbon atoms, aceto-acetic acid, is highly unstable under the conditions necessary for the reaction and does not producethe desired product. The five-carbon acid, levulinic acid, gives excellent yields. Higher acids are apparently useful, but these exist principally as laboratory curiosities and are not available in commercial quantifies. There is disclosed in prior copending applications, Serial Nos. 464,607 and 489,300, filed Qctober 25, 1954, and February 18, 1955, respectively, a number of illustrative acids that have been found to be particularlysuitable for cordingly, an additional aim of the invention is the proa vision of light-Weight three-dimensional solids possessing good structural strength and, therefore, useful in loadbearing applications.

These and other objects are accomplished by the present invention which contemplates the reaction ofa substantial amount of an isocyanate or isothiocyanate, at least half of which must contain two or more isocyanate or isothiocyanategroups per molecule, and the condensation product of an aldehyde with an aliphatic acid, having a total of at least five carbon atoms, one of which is substituted with two-hydroxyaryl groups.

It has been found that the reaction of aldehydehydroxyaryl-aliphatic acid condensates With polyisocyanates is an unusually advantageous mechanism for obtaining polymeric resinous compositions characterized by excellent protective coating and adhesive properties when used as a film, and high structural strength when cast into foam resin bodies. These condensates are especially adapted for the reaction by virtue not only of the presence in each molecule thereof of a plurality of functional groups reactive with the isocyanates, but be cause of the novel combination of hydroxyl and carboxyl radicals that make up this plurality of groupsl As will be explained more fully, both hydroxyl and carboxyl radicals condense with an isocyanate group and, thus, may serve as reactive foci leading to the formation of a resinous product; in addition, the carboxyl radical in the condensation liberates carbon dioxide which is of assistance in producing foam resin structures. Aldehydehydroxyaryl-aliphatic acid condensates useful herein are viscous or soft resinous compositions containing one or more unique symmetrical residues and tend to contribute to the reaction product 'such properties as outstanding chemical resistance and superior hardness and toughness. Chemical resistance is, for. example, or great value use, as Well as methods of preparing the same. These acids consist of the condensation products of, levulinic acid and phenol, substituted phenols, or mixtures of phenol and substituted phenols and shall, for the sake y of brevity, be referred to herein as the Diphenolic Acid. a

The term substituted phenols is used: herein to embrace phenols andphenolic' compounds wherein one or more hydrogen atoms of the phenyl nucleus is replaced by an atom or group that does not enter into, or otherwise interfere with,the condensation of' the compound with the keto-acid; Thus, for example, the nucleus may be alkylated With a methyl or other alkyl group, preferably having not more than five carbon atoms, as disclosed in the aforementioned application, Serial No. 489,300, or halogenated with bromine, fluorine, chlorine, or combinations thereof, provided that the total number of substituents, including hydroxyl groups, does not ex ceed' three; The Diphenolic Acid derived from substituted phenol'sQsuch as the alkylated phenols, are sometimes more desirable than the products obtained from unsubstituted phenols since the alkyl groups tend to provide better organic solvent solubility, flexibility, and water resistance, as Well as influencing the nature and extent of subsequent reactions for which the acids are adapted. However, the unsubstituted product is usuall more readily purified.

These hydroxyaryl-aliphatic acids react with an alde hyde, formaldehyde for example, to yield initially an alkylol condensation product. This may be illustrated by the following formula of the methylol condensation product of 1 mol of 4,4-bis(4-hydroxyphenyl)pentanoic on on Home 011 011 When phenolic compounds condense with aldehydes, the phenolic hydroxyl groups activate the aromatic nuclei at positions that are ortho and para with respect to the hydroxyl groups. The introduction of the aldehyde into the nuclei will, therefore, be at these positions, provided, of course, the carbon atoms there are coupled to hydrogen atoms. 4,4-bis(4-hydroxyphenyl)pentanoic acid has two hydrogenated carbon atoms in each of its two aromatic nuclei, so that up to 4 mols of aldehyde may be reacted readily with each mol of this acid to form an alkylol condensate. In the case of alkyl and haloderivatives of the acid, ie where alkyl groups of halogen atoms have been substituted in the aromatic nuclei of the acid, if appreciable condensation is to take place, the substitution should not be so complete as to remove all hydrogen atoms from the carbon atoms at the ortho and para positions. Upon the application of heat, the methylol groups react further and yield a resinous polybasic hydroxyacid consisting of residues of the acid linked together by methylene radicals. In those cases where the alkylol form is prepared by the introduction of aldehyde at substantially all the free ortho and para positions of the acid, polymerization is accompanied by the splitting ofi of alkylol groups and the liberation of aldehyde. A typical polymerization reaction of the material of Formula I might be illustrated as follows:

W on GE Home OHZOH heat 0H CH1 on OH 0 2 OH -CH 0H, U

\O/ \O/ CHa OHXOHaCOaH C 3 2011200211 Somewhat different products may be obtained by using the bis-hydroxyaryl-aliphatic acids in combination with other mononuclear, polynuclear, monohydric, or polyhydric phenols. Such materials are exemplified by phenol, the cresols, the xylenols, butylphenol, the naphthols, and bis(4-hydroxyphenyl)isopropylidene. These phenolic compounds may be partially condensed with an aldehyde, and then admixed with a partially condensed mixture of Diphenolic Acid and aldehyde to yield further valuable complex condensation products. Alter natively, these phenols may be added to the initial reaction mixture of bis-hydroxyaryl-aliphatic acid and aldehyde to yield after condensation a slightly modified product. The phenol-aldehyde condensates contain carboxyl. groups inaddition to alkylol hydroxyl groups and phenolic hydroxyl groups. In the more highly condensed form, where most of the alkylol groups have been dehydrated to form methylene linkages, the compositions contain primarily phenolic hydroxyl groups and carboxyl groups. These phenol-aldehyde condensates and their preparation are more fully described in a co-pending Greenlee application Serial No. 534,405, filed September 14, 1955, entitled, Phenolic Acid, Aldehyde Condensates.

For the purpose of condensingfthe Diphenolic Acid, any aldehyde can be employed that will condense with the particular hydroxyaryl substituent of the acid. Formaldehyde is universally satisfactory and is preferred.

. cyanate, and hexamethylene .diisocyanate.

It may be in the form known as formalin, a 40% aqueous solution. Formaldehyde engendering compounds, such as para-formaldehyde, trioxymethylene, and hexamethylene tetramine are also particularly suitable.

The resinous Diphenolic Acid-aldehyde condensates may conveniently be used at any stage of condensation, thus providing one wishing to formulate infusible, insoluble products with a broad range of starting materials. The condensate may be the initial reaction product consisting primarily of alkylol Diphenolic Acid, ie an A- stage resin, in which case, it would be essentially a monomer containing one carboxylic acid group, two phenolic hydroxyl groups, and one or more alcoholic hydroxyl groups per molecule. This initial aldehyde condensate may, on the other hand, be heated to couple the Diphenolic Acid nuclei and form, as a B-stage resin, a polybasic acid containing phenolic and alcoholic hydroxyl groups. All of these condensates will have substantially two phenolic hydroxyl groups for each carboxylic acid group, since so far as it can be determined the phenolic hydroxyl groups, as such, are little involved in the linking together of Diphenolic Acid molecules during condensation. The condensation must not, of course, be allowed to proceed to a point where the product is insoluble with the isocyanates with which it is to be reacted and certainly not to a C-stage resin that is insoluble and infusible. The extent of condensation should also be such as not to restrict the solubility of the product in solvents which might be used in applying a mixture of a Diphenolic Acid-aldehyde condensate and an isocyanate', as in the formation of a protective coating film.

The other component of the reaction of the present invention is an isocyanate or isothiocyanate compound. In order that a resinous product be obtained, the isocyanate or isothiocyanate compound must contain two or more isocyanate or isothiocyanate groups, a plurality of functions being essential if a chain or cross-linked structure is to be developed by condensation with the functional groups of the Diphenolic Acid. Accordingly, the principal reaction contemplated herein may be described as between a Diphenolic Acid-aldehyde condensate and a polyisocyanate having the general formula R(NCX) Where X is a chalcogen having an atomic weight less than 33, i.e., oxygen or sulfur; z is an integer of more than one; and R is a polyvalent organic radical with the number of valences being equal to z. There are numerous compounds coming within this formula that are suitable for the reaction and no attempt will be made to give an exhaustive list. The following are considered illustrative and will suggest to the expert a variety of others: alkylene diisocyanates; such as ethylene diisocyanate, trirnethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decarnethylene diisocyanate, and their corresponding sulfur analogues; cyclo-alkylene diisocyanate, such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and their corresponding sulfur analogues; aromatic diisocyanates, such as m-phenylene' diisocyanate, naphthalene diisocyanate, diphenyl-4,4'-diisocyanate, and their corresponding sulfur analogues; aliphatic-aromatic dnsocyanatea such as xylene-1,4-diisocyanate, diphenylene methane diisocyanate and their corresponding sulfur analogues; heterodiisoand diisothiocyanates, such as SCNCH OcH NCS and SCNCI -I SCH NCS; and isocyanates and isothiocyanates having more than two isocyanate -or isothiocyanate groups, such as benzene 1,2,4- triisocyanate, 1,2,Z-triisocyanatobutane, andtoluene triisocyanate. From among these and other polyisocyanates andpolyisothiocyanates, the following are preferred rgely byreason of their ready commercial availability: toluene 2,4 diisocyanate, toluene 2,6 diisocyanate, methylene .bis (4-phenyl isocyanate), 3,3. bitolylene 4.4 diiso- In order to simplify the remainder of the discussion, the repetitious rgi iifi of both the oxygen and splfiir forms will be dispensed with; only the oxygen compound will be given but will be understood as embracing the corresponding sulfur analogue.

White, as has already been mentioned, the principal reaction requires a polyisocyanate compound, it is desirable for certain applications to modify the product by using, in: addition, a minor portion of a monoisocyanate. Some of the reaction products of Diphenolic Acid with polyisocyanates. alone are brittle infusible products; on the other hand, flexible infusible products may be frequently obtained by the addition to the reaction mixture of a proper amount and type of monoisocyanate. Examples of suitable monoi'socyanate' are octadecylisocyanate, hexyl isocyauate, phenyl isocyanate and naphthalene isocyanate, to mention just. a few of the simpler compounds. Flexibility is particularly apparent where longchain compounds, i.e., havingmore than 11 carbons, are employed. Unsaturated monoisocyanates are also suitable and provide an additional aid to conversion or curing. The amount of the monocompound that is added to the acid and polyisocyanate as a modifier will vary depending upon the characteristics described in the product. Asa general rule, there should be present a greater amount of the poly-compoundthat the monocompound, which is to say, that the monoisocyanate should be less than 50% of the total of all isocyanates in the reaction mixture. If a more rigid, brittle material is sought, the quantity of the mono-form should be decreased while, if more flexibility is the desideratum, it should be increased toward the upper limit just mentioned. The functional group of the mono-form may react with the carboxyl or hydroxyl groups of the condensate to reduce cross-linking between adjacent molecules of the polymer and thereby enhance the softness and pliability of the product in proportion to the amount present, or a functional group of one or more molecules of the monoisocyanate may react with methylol groups of the condensate, and, thus, preclude further growth of the chain.

The general chemistry of the present reaction appears to be basically simple. It is Well known that isocyanates,

react with both phenolic hydroxyl groups and carboxylic acid groups. The reaction of a diisocyanate, R(NCO) with a phenolic or aliphatic hydroxyl compound ROH, proceeds in the following manner:

In similar fashion, the reaction between a diisocyanate and a carboxylic acid, RCOOI-I, is as follows:

It will be seen that, if the phenolic compound contains two hydroxyl groups or if the carboxylic acid contains;

two acid groups, the resulting product in either case would be polymeric. Likewise, it will be observed that if a compound is used containing both carboxyl groups and phenolic hydroxyl groups, there is the possibility of simultaneous reaction of both with the isocyanate to give polymeric compounds. tion with a carboxyl-containing compound gives, as a byproduct of the reaction, carbon dioxide which may be used to form cellular structures in those reaction products which are intended to be three-dimensional structures.

Applying these general considerations to the reactants proposed herein, a Diphenolic Acid-aldehyde condensate and a polyisocyanate R(NCO),, it will be appreciated that the directions in which the reaction might go are too varied to be readily illustrated. An isocyanate residue may bridge phenolic or methylol hydroxylgroups of two molecules of the condensate, carboxyl groups of two molecules, or a hydroxyl group of oneand a carboxyl group of another. The nature and extent of the reactions which actually. occur are somewhat dependent upon the amount of isocyanate available for reaction and the distribution of the isocyanate molecules among the con- It will also be observed that the reac' nace with the present inventioninvolves merely the addison, a preferred range is 2:1 to 1:2 of condensate to isocyanate on equivalent basis with a 1:1 ratio being most desired. As a; general rule, it can. be postulated.

that as the proportion of condensate is increased, the polymer becomes more rigid and hard while, conversely, asthe proportion of isocyanate. is increased, the polymer becomes: more flexible, this being particularly true. where the functional. groups of. the isocyanateare separated by fairly long chains so that the acid nuclei are spaced relatively large distances apart within the molecule of the polymer, which thus assumes a more or less linear configuration. On the other hand, where the isocyanate is of a tightly knit, cyclic structure, the tendency is toward enhanced rigidity and brittleness;

If a monoisocyanatc -RNCX- is employed along. with the polyisocyanate, the number of reactive foci of the condensate available to the functional groups of the poly-compoundis lessened. In: arriving at the amounts of reactants; to be utilized, the mono-compound must therefore be considered, and in such case the equivalent Weight of the isocyanate is the total of the equivalent weights of the monoand poly-compounds.

In. general, the procedure by which protective coating films and molding compositions are prepared in accordtion at ordinary temperatures of the condensate to the isocyanate, admixing and converting the mixture by ex posure either to normal temperatures or to heat. In some cases, it is desirable to dilute either or both of the reactants, e.g.,. tolower the viscosity of the mixture and, thus, vary the filmthickness of a single coat. Any solvent that is inert -to both the condensate and isocyanate maybe used, an example being methyl ethyl ketone amongv many others. The mixture of reactants, either diluted or not, has been found to be quite stable for moderate periods at normal temperatures. Such stability is a feature-of some importance as it permits large quantities of themixture to be made up at one time and then used as needed. For heat cure, temperatures of about 225 C. for times of about one hour to about five minutes have been found satisfactory. For a normal temperature cure, it is preferred that any of the well known conversion catalysts for reactions of this type, such as triethanolamine, 'be added in small amounts in order to reducethe amount of time needed for the film to harden. When early conversion is of no special advantage, the catalyst nraybe' dispensed with. As the examples show, the characteristics of the cured films vary somewhat withthe type and amount of the isocyanate employed, with some being; better than others, as would ordinarily be expected. As a whole, however, the films possess characteristicsthat compare favorably with many other available materials so that the product of the invention is quite useful for a variety of purposes.

Where solid foam or cellular structures are desired, they may be obtained by mixing the condensate with a suitable conversion catalyst, of which triethanolamine is again an example, in anlappropriate reaction vessel, adding the' isocyanate while agitating, allowing the mixture to foam unimpeded, and converting by heating, as in a. draft oven, at atemperature of about 85-150 .0. or moref'or frornaqabout 5-30 minutes, or by normal temperatures for'. much longer periods. Although not essentiall, it is usually desirable to employ anuemulsifier in specified for each acid. The isocyanate equiValenhisfw defined as the weight of the acid which will react. with one equivalent of theisocyanateand will be of assistance in selecting actual amountsof the acid that should be used. The method. usedjnwdetermining the observed values as listed involves reacting a sample. .of the. acid...

with an excess of toluene-2, 4-diisocyanate and then determining the excess isocyanate by reaction with dimbutylamine. Specifically; the technique used is as follows:

To 25 ml. of methyl isobutylketone is added 3Lgrams of toluene-2,4-diisocyanate previously standardized against di-n-butylamine and a weight of the acid suclrthat they diisocyanate is present ;in approximately 100%,. excess. To this mixture is addedjtriethylamine in an am'ouritequal i "to 1% of the total weight of isocyanate and the acid. ..Themixtureisrefluxedfor a period of one hour. After cooling. to room..temperature,. the condenser walls are rinsed with about 25 ml. of redistilled toluene. To this mixture is 'addedZSwmlJofZ N 1di-nrbutylamine... .This mixture is warmed to the boiling point, allowed to stand for .onehourat which point 75 ml. of methanol is added, and the excess di-n-butylamine back-titrated with 1 N alcoholic hydrochloric acid. By carrying out the preparation of the acids with. great care, values ator approach ing the theoretical can be achieved.

The acid number given for each acid has its usual meaning; which is the number of milligrams of potassium hydroxide necessary to neutralize the acid content of one gram of the sample, and provides an indication of the degree of acidity of the product.

TABLE 11 Representative isiocyanates Amine equivalent Commercialsource, trade name, and abbreviation 1 Structure i .Qbserved Theory E. I. du Pont de Nemours &- 00., InegHylenaT; Hy '1 90.62 87.07

i "loluene-zA-diisocyanate 1 11.11111 rontaarrein mseoo n egn i neimn QC.N-@-(|l-NOO 139198 125.12

Methylene bisg phenyl isdcyanatel V v jMel" Me 3 National Aniline Div.; Nacconate200; Nearing "L.- QQN D O NCO 132.78 132.13

i 3 3. Bitolylene-ggtf-diisoeyanate 1 N00 w Mobay Chemical 00.; Mondtiri rs; MoNs -J 116.58 105.09

Naphthylene-l,6-diisocyanate Mobay Chemical CojMondm'LMi MO TMWQQ; 107.78 123.45

. 5i Q"Tritolyliiiethanetriisocyanate 1. Mam OhemicalCo.;MondurHX;M0 11x -z. :foempu' imco 103.39 54.91 i 3 Hexapietliylenediisccyanate 1, l I Approx. Mflbay Chemical 00.; MondunBrMO P- 119: 7 11a.

heia f x aa a.

TABLE II-Continued Representative isocyanates-Continued Amine equivalent Commercial source, trade name, and abbreviation Structure Observed Theory Approx.

Mobay Chemical 00.; Mondur NP; M0 NP 169 169 Naphthyl isocyanate Shell Development 00.; Duronedlisooyanate; Dun. 0 CN- NO 0 111. 22 108. 12

OH; H,

2,3,5,6-tetramethyl-1,4-benezene diisooyanate It will be noted that an observed and theoretical amine equivalent 'is specified for each isocyanate. The amine equivalent refers to the weight of the isocyanate containing one isocyanate group and reacting with one mole of di-n-butylamine. Since the isocyanates available commercially are not necessarily chemically pure, the observed values were obtained for use as a guide in formulating reaction products therefrom as these values provide a measure of the actual purity of each compound.

The analytical procedure used to determine amine equivalents of diisocyanates is found in Monsanto Chemical Companys Technical Bulletin #P-lZS and is generally as follows:

Twenty-five milliliters of redistilled toluene and ml. of approximately 2 N di-n-butylamine were placed in a carefully cleaned and dried 250 ml. or 500 ml. Erlenmeyer flask. The sample of diisocyanate was drawn into a warmed glass bulb and the neck sealed off in a flame. Sample weight is determined by the difference in weight between the empty and the filled bulb. The bulb wasimmersed in the Erlenmeyer flask and crushed beneath the surface of the liquid. The solution was heated to boiling and, allowed to cool 1 hour. 100 m1. of technical methanol and 0.5 ml. of bromophenol blue indicator was added. It was then titrated with 1 N HCl to a yellow end point. The indicator /was prepared by taking 0.1 g. of bromophenol blue, 1.5 ml. of 0.1 N NaOH diluted 25 with 100 ml. ofdistilled H O. The average precision demonstrated by these determinations was 14.29%.

The following examples, presented in tabular form to "'conserve space, illustrated the conversion of mixtures of Diphenolic Acid and polyisocyanates alone and modified with a monoisocyanate to insoluble, infusible prodgredients together were applied to glass panels at .002"

wet film thickness. The table gives the heat treatment used for conversion. All parts are by weight.

It will be understood that certain tabulated examples are superior in some respects to other examples, the

purpose of the table is to give an indication ofthe properties possible with varying compositions. With a particular application in mind, the composition may be formulated accordingly to obtain the desired characteristics. In Table 111, Examples XII, XIII, XIV and XVI have been found to be particularly well-suited for protective coatings.

TABLE III Examples of the invention as a coating Conversion Wlthstood in hours Acid Polylso- Monolso- Ex. No. condensate Parts eyanato Parts cyanate Parts Solvent 5% Time Tenp H 0 at aqueous (hrs.) 0 Na l MEK is abbreviation for methyl ethyl ketone.

- i-ng examples were prepared:

EXAMPLE XX 526 parts of theacid condensate 1 were heated until melted and thereafter mixed with 26. parts of polyoxyethylene sorbitan mono-oleate, an emulsifier sold under the trade-nameT een'SQ byfAtlas Powder Company, and 3.6 parts of triethylamine-to form a homogeneous mixture. Then, 906 parts of toluene-2,4-diisocyanate were stirred into the mixture while the latter was maintained at 110 C. The evolution of foam occurred almost instantaneously and the mixture solidified within a short time, although heating was continued for about 5 minutes to insure that a complete cure had been obtained. The result was a dark brown, brittle, rigid foam having cells of irregular size dispersed throughout.

EXAMPLE XXI Example XX was repeated except that 1034 parts of hexamethylene diisocyanate were employed as the isocyanate. The product was a yellow, hard, rigid, tough foam having an irregular cell structure.

EXAMPLE XXII EXAMPLE XXIII Example XX was repeated except that 620 parts of the acid condensate AC 4 were substituted, the amount of the isocyanate was decreased to 453 parts and the amount of the emulsifier was increased to 31 parts. The foam that was produced was rigid, tough and brittle, with a yellow color and an irregular cell structure.

The aforegoing examples, both as to films and foams, are furnished only for the guidance of those seeking to practice the invention and not for the purpose of defining the boundaries in which it is operative. The numerous other embodiments are possible and will be suggested by these relatively few illustrations.

Although the examples describe the preparation of products in which the reaction is allowed to proceed to the point where the product is infusible and insoluble, it will be appreciated that the reaction could be terminated short of this point to yield intermediate products.

For certain applications, it may be desirable to carry the reaction to an intermediate stage and eifect the final cure by exposure either to room temperature for a long period of time or to a further heat treatment. It will also be understood that although the examples in the tables were converted to the insoluble, infusible state by means of heat, this was done largely in the interest of saving time and the same result can ordinarily be obtained at room temperature for much longer periods of time.

It is contemplated by the invention that various inactive ingredients, such as fillers, pigments and plasticizers can be added to the reaction mixture to modify the product in known ways. For example, the admixture of a pigment would be suggested where the produce was to be used as a decorative coating as a replacement for paint. Inert fillers, such as siliceous and metallic powders might be added where the specific application demands a product having unusual structural strength or. resistance to heat.

It, is claimed and desired to secure by Letters Patent:

"1. A new composition of matter. comprising a polyurethane condensation product of (A) a compound of the general formula R(NCX) wherein R is an organic radical having a valency equal to z, X is a chalcogen 14 having an atomic weight of less than 3 3, and: is all integer having a value. of morethan 1; and. (B) f a resinous polybasic acid which is the condensation prod uQt of (a) formaldehyde and (b) a pentanoic. acid eonsisting essentially .of 4,4 bis(4-hydroxyaryl)pentanoic acid, wherein the hydroxyaryl radical is a hydroxyphenyl radicalandis free from substitutents other than alkyl groups of from 1 to 5 carbon. atoms with said hydroxyphenyl radical having hydrogen on at least one position ortho to the hydroxyh'wherein the ratio of (a) 'to (b) is from 1 to 4 moles of (a) per mole of (b), and having a ratio of (A) to (B) of from 1:5 to 5:1 on an equivalent, weight basis.

2. A new composition of matter comprising a polyurethane condensation product of (A) a compound selected from the class consisting of organic p0lyiso cyanates antd polyisothiocyanates; and (B) a resinous polybasic acid which is the condensation product of (a) formaldehyde and (b) 4,4 bis(4-hydroxyphenyl)- pentanoic acid wherein the ratio of (a) to (b) is from 1 to 4 moles of a (a) per mole of (b), and having a ratio of (A) to (B) of from 1:5 to 5:1 on an equivalent weight basis.

3. The composition of claim 1 wherein (A) and (B) are reacted in amounts on an equivalent weight basis having a ratio of (A) to (B) of from 1:2 to 2:1.

4. A new composition of matter comprising a polyurethane condensation product of (A) a compound of the general formula R(NCX)Z wherein R is an organic radical having a valency equal to z, X is a chalcogen having an atomic weight of less than 33, and z is an integer having a value of more than 1; (B) a resinous polybasic acid which is the condensation product of (a) formaldehyde and (b) a pentanoic acid consisting essentially of 4,4 bis(4-hydroxyaryl)pentanoic acid, wherein the hydroxyaryl radical is a 'hydroxyphenyl radical and is free from substituents other than alkyl groups of from 1 to 5 carbon atoms, with said hydroxyphenyl radical having hydrogen on at least one position ortho to the hydroxyl, wherein the ratio of (a) to (b) is from 1 to 4 moles of (a) per mole of (b) and having a ratio of (A) to (B) of from 1:5 to 5:1 on an equivalent weight basis; and (C) up to about 5% of the total weight of (A) and (B) of water.

5. A method of preparing a new composition of mat ter which comprises admixing (A) a compound of the general formula R(NCX),, wherein R is an organic radical having a valency equal to z, X is a chalcogen having an atomic weight of less than 33, and z is an integer having a value of more than 1; (B) a resinous polybasic acid which is the condensation product of (a) formaldehyde and (b) .a pentanoic acid consisting essentially of 4,4 bis(4-hydroxyaryl)pentanoic acid, wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of from 1 to 5 carbon atoms, with said hydroxyphenyl radical having hydrogen on at least one position ortho to the hydroxyl, wherein the ratio of (a) to (b) is from 1 to 4 moles of (a) per mole of (b), and having a ratio of (A) to (B) of from about 1:5 to 5:1, and converting said mixture to an insoluble infusible resin.

6. A method of claim 5 wherein said mixture is converted by air drying at room temperature.

7. The composition of claim 1 where the pentanoic acid of (B) consists essentially of 4,4 bis(4-hydroxyaryl)pentanoic acid wherein the hydroxyaryl radical is a hydroxpyhenyl radical and is free from substituents other than alkyl groups of one carbon atom.

8. The composition of claim 1 wherein R of (A) is an organic aromatic radical.

9. The composition of claim 1 wherein R of (A) is an organic aliphatic radical;

10. A new composition of matter comprising a polyurethane condensation product of (A) a mixture of organic monoisocyanates and polyisocyanates wherein at least 50% of the mixture is a polyisocyanate and (B) a ratio o (B) o from t0 on an a resinous polybasic acid which is the condensation prodq lv en Welght b85185 uct of (a) formaldehyde and (b) a pentanoic acid consisting essentially of 4,4 bis(4-hydroxyaryl)pentanoic References Cited in the file of this Patent acid, wherein the hydroxyaryl radical is a hydroxyphenyl 5 FOREIGN PATENTS radical and is free from substituents other than alkyl 901,768 France 5 45 groups of from 1 to 5 carbon atoms, with said hydroxyphenyl radical haying hydrogen on at least one position i OTHER REFERENCES ortho to the hydroxyl, wherein the ratio of (a) to (b) Bader et al.: Jour. Am. Chem. Soc., vol. 76, pages is from 1 to 4 moles of (a) per mole of (b), and hav- 10 4465-4466. (Copy in Sci. Libr.)

fin-

UNITED STATES PATENT {OFFICE CERTIFICATE OF CORRECTION Patent No. 2,907,750 October 6 1959 Sylvan Green lee It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 59, for "L l-bis"- read 4,4-bis column 4 line 72, for "4.4?" read 4,4 column 6, line ll, for "th" read the lines 35 and 36., for "-accordnace" read accordance column 7, lines 1 and 2, for "reactance" read reactants column 8', Table I the italicized heading thereof for "Representative diphenolic acidaldehyde condensate read Representative Diphenolic Acid-aldehyde condensate same column 8, same Table I, second column thereof, lines 10 53,, and 62 for "diphenolic acid", each occurrence, read Diphenolic Acid column 13, lines 65 and 66, for produce" read product Signed and sealed this 4th day of October 1960a (SEAL) Atte-st:

KARL H, AXLINE ROBERT C. WATSON Attesting Officer Commissioner of Patents 

1. A NEW COMPOSITION OF MATTER COMPRISING A POLYURETHANE CONDENSATION PRODUCT OF (A) A COMPOUND OF THE GENERAL FORMULA R(NCX)Z, WHEREIN R IS AN ORGANIC RADICAL HAVING A VALENCY EQUAL TO Z, X IS A CHALOCOGEN HAVING AN ATOMIC WEIGHT OF LESS THAN 33, AND Z IS AN INTEGER HAVING A VALUE OF MORE THAN 1; AND (B) A RESINOUS POLYBASIC ACID WHICH IS THE CONDENSATION PRODUCT OF (A) FORMALDEHYDE AND (B) A PENTANOIC ACID CONSISTING ESSENTIALLY OF 4,4 BIS(4-HYDROXYARYL)PENTANOIC ACID, WHEREIN THE HYDROXYARYL RADICAL IS A HYDROXYPHENYL RADICAL AND IS FREE FROM SUBSTITUENTS OTHER THAN ALKYL GROUPS OF FROM 1 TO 5 CARBON ATOMS, WITH SAID HYDROXYPHENYL RADICAL HAVING HYDROGEN ON AT LEAST ONE POSITION ORTHO TO THE HYDROXYL, WHEREIN THE RATIO OF (A) TO (B) IS FROM 1 TO 4 MOLES OF (A) PER MOLE OF (B), AND HAVING A RATIO OF (A) TO (B) OF FROM 1:5 TO 5:1 ON AN EQUIVALENT WEIGHT BASIS. 